The song that gave the title to the album was "Orange Blossom Special", released previous to the album, it became a success. At the time it was recorded, the authorship of the song was not widely known, being commonly covered by diverse artists. Cash learned from Maybelle Carter that the song was written by Ervin T. Rouse, who Cash later met during a show in Miami, Florida. Cash's recording is unusual in his repertoire for featuring a tenor saxophone solo by Boots Randolph, an instrument (and musician) rarely spotlighted on Cash's recordings.

The album also contains three covers of Bob Dylan songs, that he gave Cash after a concert in Newport, Rhode Island. "It Ain't Me Babe", "Don't Think Twice, it's Alright" and "Mama, You've Been on My Mind". The last one was only recorded by Dylan as a demo, but it was first released in an album by Cash. Cash had previously borrowed the melody of "Don't Think Twice" for his recording "Understand Your Man."

Due to the acclaim that the cover of the song "Orange Blossom Special" received from the audiences that attended live concerts of Cash, a single of the song was released previous to the album, in February 1965 reaching number three in the Billboard singles.[3] During the mid 1960s, the authorship of the song was not widely known. Cash asked Maybelle Carter during the recording session about the original author, Carter stated that the song was written by Ervin T. Rouse and his brother Gordon. Carter also told Cash that the songwriter resided in Florida. Cash called Florida disk jockey Jim Brooker, who told him that he lived with the Seminoles on the Everglades. In order to locate him, Brooker announced on air during his radio show, that if Rouse was listening to call the station to give him the phone number of Cash. Rouse called the station and contacted Cash who told him that he would be soon in Miami, Florida for a scheduled concert.[4][5]

During an intermission of the show in Miami, a man approached Cash backstage claiming to be Ervin Rouse. Cash recalled hearing the name but he could not remember who Rouse was. After clarifying that he had written a few songs, he remarked that one he co-wrote with his brother, named "The Special", was particularly successful. Cash recognized that he was talking about Orange Blossom Special. Cash believed the man, who actually was Rouse, that he had traveled from his house in the everglades in a custom-made swamp buggy to the house of his sister in Miami, where he borrowed her bicycle to ride ten miles to be at the concert. Cash invited the man to perform the song with him in the concert, receiving the acclaim of the audience. Later Rouse stated: "The Special belongs to everybody by now, I guess, but it used to be my best number"[3][5][6] Cash's back-cover album notes for Orange Blossom Special are devoted to describing his meeting with Rouse.

Billboard wrote: "Cash is in fine form here and he has been coupled with a great selection of material. Cash displays a sense of drama and wit".[10] Meanwhile, Western Folklore also praised the album as well as the recognition of the original author of the title song: "Johnny Cash offers an interesting collection of songs, partially reflecting the Folk Song Revival's influence, in Orange Blossom Special. While the album is good, the notes are even better for they give information previously unreported on the title tune of the album and its credited composer, Ervin Rouse."[11] AllMusic later wrote about the album: "Even if the best and most popular of the songs on this 1965 album are the ones most likely to show up on greatest-hits compilations, it certainly rates as one of Cash's finer non-greatest-hits releases".[1]

The song "Orange Blossom Special" later became a regular part of Cash's concerts, with Cash performing both harmonica parts himself, usually with a dual-harmonica technique. During a performance included on his At Folsom Prison live album, Cash jokes that the song requires him to "change harmonicas faster than kiss[ing] a duck".